Phenylethynyl containing reactive additives

ABSTRACT

Phenylethynyl containing reactive additives were prepared from aromatic diamines containing phenylethynyl groups and various ratios of phthalic anhydride and 4-phenylethynylphthalic anhydride in glacial acetic acid to form the imide in one step or in N-methyl-2-pyrrolidinone to form the amide acid intermediate. The reactive additives were mixed in various amounts (10% to 90%) with oligomers containing either terminal or pendent phenylethynyl groups (or both) to reduce the melt viscosity and thereby enhance processability. Upon thermal cure, the additives react and become chemically incorporated into the matrix and effect an increase in crosslink density relative to that of the host resin. This resultant increase in crosslink density has advantageous consequences on the cured resin properties such as higher glass transition temperature and higher modulus as compared to that of the host resin.

CROSS-REFERENCE

This patent application is related to commonly owned patent applicationSer. No. 09/310,686, filed Apr. 13, 1999, now U.S. Pat. No. 6,124,035,and is a divisional application of co-pending patent application Ser.No. 09/290,295, filed Apr. 13, 1999.

ORIGIN OF THE INVENTION

The invention described herein was made by employees of the UnitedStates Government and may be manufactured and used by or for theGovernment or government purposes without payment of any royaltiestherein or therefor.

BACKGROUND OF THE INVENTION

A variety of monomers, oligomers and polymers containing ethynyl(acetylenic) and substituted ethynyl (i.e., phenylethynyl) groups havebeen reported. The ethynyl groups in the polymer are either pendent tothe chain, in the chain or at the chain ends. Many of these materialshave been used to prepare coatings, moldings, adhesives and composites[P. M. Hergenrother, “Acetylene Terminated Prepolymers” in Encyclopediaof Polymer Science and Engineering, John Wiley and Sons, New York, Vol.1, 61 (1985)]. Good processability by either solution casting and/orcompression molding have been observed for the ethynyl and substitutedethynyl containing materials. In general, thermally cured ethynyl andsubstituted ethynyl containing materials exhibit a favorable combinationof physical and mechanical properties. Some ethynyl endcapped materialssuch as the Thermid® resins are commercially available (National Starchand Chemical Co., Bridgewater, N.J. 08807). Other systems such asacetylene terminated sulfone have undergone extensive evaluation asmatrix resins [M. G. Maximovich, S. C. Lockerby, F. E. Arnold and G. A.Loughran, Sci. Adv. Matls. Proc. Eng. Ser., 23, 490 (1978) and G. A.Loughran, A. Wereta and F. E. Arnold, U.S. Pat. No. 4,131,625, 12/78 toU.S. Air Force].

Phenylethynyl containing amines have been used to terminate imideoligomers [F. W. Harris, A. Pamidimuhkala, R. Gupta, S. Das, T. Wu, G.Mock, Poly. Prep., 24 (2), 325, 1983; F. W. Harris, A. Pamidimuhkala, R.Gupta, S. Das, T. Wu, G. Mock, Macromol. Sci.-Chem., A21 (8&9), 1117(1984); C. W. Paul, R. A. Shultz, and S. P. Fenelli, “High TemperatureCuring Endcaps for Polyimide Oligomers” in Advances in Polyimide Scienceand Technology, (Ed. C. Feger, M. M. Khoyasteh, and M. S. Htoo),Technomic Publishing Co., Inc., Lancaster, Pa., 1993, p. 220; R. G.Bryant, B. J. Jensen, P. M. Hergenrother, Poly. Prepr., 34(1), 566, 1993]. Imide oligomers terminated with ethynyl phthalic anhydride [P. M.Hergenrother, Poly. Prepr., 21 (1), 81, 1980 ], substituted ethynylphthalic anhydride [S. Hino, S. Sato, K. Kora, and O. Suzuki, Jpn. KokaiTokyo Koho Japanese Patent No. 63,196,564. Aug. 15, 1988; Chem. Abstr.,115573 w, 110, (1989)] and phenylethynyl containing phthalic anhydrideshave been reported. Imide oligomers containing pendent substitutedethynyl groups [F. W. Harris, S. M. Padaki, and S. Varaprath, Poly.Prepr., 21 (1), 3, 1980 (abstract only); B. J. Jensen, P. M.Hergenrother and G. Nwokogu, Polymer, 34 (3), 630, 1993; B. J. Jensenand P. M. Hergenrother, U.S. Pat. No. 5,344,982 (Sep. 6, 1994)] havebeen reported. See also J. E. McGrath and G. W. Meyer, U.S. Pat. No.4,493,002 (Feb. 20, 1996), J. G. Smith, Jr. Adhesion SocietyProceedings, Vol. 19, 29-32 (1996) and J. W. Connell, J. G. Smith, Jr.And P. M. Hergenrother, Society for the Advancement of Materials andProcess Engineering Proceedings, Vol. 41, 1102-1112 (1996).

High temperature resins are used in a variety of aerospace andnon-aerospace applications. Generally these materials require highpressures (>200 psi) to form adhesive bonds, well consolidated moldingsor fiber reinforced composite laminates. However, there exists a needfor novel high temperature resins that can be processed at low pressuresand without an autoclave (i.e., under vacuum bag conditions-˜15 psi)while maintaining excellent mechanical properties.

It is a primary object of the present invention to provide novelphenylethynyl containing reactive additives (PERAs) which can be usedwith any phenylethynyl containing polymer, co-polymer, oligomers orco-oligomers to decrease melt flow and consequently processing pressuresrequired to fabricate molded parts, adhesive bonds, and fiber reinforcedcomposite parts.

SUMMARY OF THE INVENTION

According to the present invention the forgoing and additional objectsare obtained by synthesizing amide acid and imide phenylethynyl reactiveadditives, subsequently adding them to phenylethynyl containingpolymers, co-polymers, oligomers and co-oligomers in solution or bymixing dry imide powder of the reactive additive with phenylethynylcontaining oligomer powder. These species can be combined in severaldifferent ways: as solutions of amide acid of the phenylethynylcontaining reactive additive (PERA) to a solution of the phenylethynylcontaining polymer, co-polymer, oligomer, co-oligomer; as solutions ofthe imide of the PERA to solutions of the phenylethynyl containingpolymer, co-polymer, oligomer, co-oligomer and by dry mixing of theimide powder of the PERA to the dry powder of the phenylethynylcontaining polymer, co-polymer, oligomer, co-oligomer. The effect ofthese reactive additives on the processability and properties on theresin systems depends upon the form of the PERA (i.e., imide vs. amideacid) used.

The PERA reduce the melt viscosity of the phenylethynyl containingpolymer, co-polymer, oligomer, and co-oligomer to which they are addedand thereby reduce the processing pressures required to form theadhesive bonds, consolidated filled or unfilled moldings or to fabricatefiber reinforced composite laminates. Upon thermal cure the PERAs reactwith themselves as well as with the phenylethynyl containing host resinand thereby become chemically incorporated into the resin system. Theeffect on mechanical properties, relative to those of the host resin,are dependent on the amount of PERA used, but typically result in higherT_(g)s, higher mechanical properties such as modulus and compressiveproperties as well as higher retention of these mechanical properties atelevated temperatures without significantly reducing toughness or damagetolerance (as determined by compression after impact strengths ofquasi-isotropic laminates).

BRIEF DESCRIPTION OF THE DRAWING

For a more complete understanding of the present invention, includingits objects and attending benefits, reference should be made to theDescription of the Preferred Embodiments, which is set forth in detailbelow. This Detailed Description should be read together with theaccompanying drawings, wherein:

FIG. 1 is an equation showing the preparation of phenylethynyl reactiveadditives according to the present invention.

FIG. 2 is an equation showing the preparation of Random Amide Acid andImide Co-oligomers (PETI-5).

FIG. 3 illustrates the effect of PERA-1 on the melt viscosity of PETI-5imide powder.

FIG. 4 is an equation showing the preparation of Random Amide Acid andImide Co-oligomers (PTPEI-1).

FIG. 5 is an equation showing the preparation of Random Amide Acid andImide Co-oligomers (PPEI-1).

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Phenylethynyl containing reactive additives are prepared from aromaticdiamines containing phenylethynyl groups and various ratios of phthalicanhydride (PA) and 4-phenylethynylphthalic anhydride (PEPA) as depictedin FIG. 1. The PERAs may be used in both the amide acid and the imideform to lower the melt viscosity of the host phenylethynyl containingresin. The PERA amide acids are prepared by reacting a diaminecontaining phenylethynyl groups with a mixture of PA and PEPA inN-methyl-2-pyrrolidinone (NMP) at room temperature under nitrogen. Theproducts remain soluble in NMP. The PERA imide products are preparedfrom the amide acid intermediate in NMP by adding toluene and heatingthe mixture to reflux (˜150-160° C.) under nitrogen or in one step byreacting a diamine containing phenylethynyl groups with a mixture of PAand PEPA in refluxing glacial acetic acid. The imide products aresoluble in NMP up to 50% solids by weight. Since all of the productsfrom the reaction used to prepare the PERAs contain at least onephenylethynyl group, upon thermal cure with a phenylethynyl containinghost resin, the PERAs react and become chemically incorporated onto thematrix and thus cannot migrate or leach out.

Three different PERAs were prepared and evaluated. PERA-1 was preparedfrom 3,5-diamino-4′-phenylethynylbenzophenone and an equimolar amount ofPA and PEPA in refluxing glacial acetic acid. The amide acid of PERA-1was prepared from 3,5-diamino-4′-phenylethynylbenzophenone and an equalmolar amount of PA and PEPA in NMP at 23° C. under nitrogen. PERA-2 wasprepared from 3,5-diamino-4′-phenylethynylbenzophenone (1.0 mole) and PA(1.5 mole) and PEPA (0.5 mole) in refluxing glacial acetic acid. PERA-3was prepared from 3,5-diamino-4′-phenylethynylbenzophenone (1.0 mole)and PA (0.5 mole) and PEPA (1.5 mole) in refluxing glacial acetic acid.The PERAs were added to the host resin, which can be any polymer,co-polymer, oligomer, or co-oligomer containing phenylethynyl groups, inorder to reduce the melt flow and increase the ease of processability.The phenylethynyl groups of the host resin can be either pendent,terminal or in the backbone or any combination thereof. The amount ofadditive to bring about the desired reduction in melt viscosity wasdependent on the melt viscosity of the host resin. The PERAs (both amideacid and imide forms) were typically added as solid solutions (i.e., drypowder) to a solid solution of the phenylethynyl containing host resinand were subsequently processed into the desired form.

In one aspect the present invention is the process of addingphenylethynyl reactive additives (PERAs) to phenylethynyl containingpolymers, co-polymers, oligomers and co-oligomers in solution or bymixing dry imide powder of the reactive additive with the phenylethynylcontaining oligomer powder in order to reduce the melt flow and increasethe ease of processability.

The best results were obtained with formulations of PERA-1 and aphenylethynyl terminated amide acid co-oligomer with a calculated numberaverage molecular weight of 5000 g/mole (designated as PETI-5). ThePETI-5 amide acid 5 solution in NMP and imide powder were prepared from3,4,3′,4′-biphenyltetracarboxylic dianhydride (BPDA) (0.91 mole),3,4′-oxydianiline (3,4′-ODA), 1,3-bis(3-aminophenoxy) benzene (1,3-APB)(0.15 mole) and 4-phenylethynylphthalic anhydride (PEPA) (0.18 mole)according to a procedure previously reported by P. M. Hergenrother andJ. G. Smith, Jr., Polymer Preprints, 35(1), 353, 1994. The syntheticscheme is depicted in FIG. 2. PERA-1 in the imide form was physicallymixed with PETI-5 imide powder in concentrations ranging from 10% to 90%by weight and the resultant formulations characterized for complex meltviscosity and thermal properties. The data is presented in Table 1.

TABLE 1 Characterization of Physically Mixed Imide Powders of PERA-1 andPETI-5 Thermal Thermal Minimum PETI- Transition Transition Complex Temp.of PERA-1 5, Temp., Temp., ° C. Melt Minimum Weight Weight ° C. Cured*(Melting Viscosity, Viscosity, % % Initial temp.) poise ° C. 100 0 182ND 0.1 270 90 10 182 ND 14 270 80 20 183 ND 21 373 65 35 182 ND 53 37050 50 182 ND 500 371 35 65 183 ND 4700 372 20 80 182 273 (393) 5600 36915 85 185 276 (390) 44700 371 10 90 183 278 (392) 52000 371 0 100 235250 (387) 56500 371 *Cured 1 hour at 350° C. in a sealed aluminum pan.ND = Not detected by DSC

The data in Table 1 indicates that the most drastic reduction in complexmelt viscosity occurred with a PERA-1 loading of 20 weight %. Higherloading results in a continued decrease in complex melt viscosity asshown in FIG. 3. The composition containing 10 weight % PETI-5 exhibitsa dramatic reduction in the temperature at which the lowest complex meltviscosity is observed, decreasing from ˜371° C. to ˜270 ° C.

The imide of PERA-1 was mixed at a 20 weight % loading with the amideacid of PETI-5 in NMP at a concentration of ˜35% weight/weight. To thissolution was added toluene and the mixture was heated under a Dean Starktrap to remove the water of imidization. The PETI-5 imide powderprecipitated during this imidization. The mixture was poured into waterand the solid isolated and dried. This material exhibited an initialthermal transition ˜180° C. and a T_(g) of 272° C. and a meltingtransition of 443° C. after curing for one hour at 350° C. The minimumcomplex melt viscosity was 14500 poise at 367° C.

Unidirectional carbon fiber (IM-7, unsized, 3 k tow) prepeg was preparedby solution coating from an NMP solution (35% solids) of the imide ofPERA-1 (20%)/PETI-5 amide acid (80%). The prepeg was processed intocomposite laminates under 50 psi whereas composite laminates of the samelay-up and number of plys fabricated from PETI-5 prepeg are typicallyprocessed under 200 psi. Laminate data is presented in Table 2. Theeffect of the PERA-1 concentration on the minimum melt viscosity ofPETI-5 imide powder is presented graphically in FIG. 3.

TABLE 2 IM-7 Laminate Properties* PETI-5 (200 psi PERA-1/PETI-5 20/80Property processing) (50 psi processing) T_(g), ° C. (G′) 270 290 OpenHole Compression Strength, Ksi 23° C. 56.5 58.4 177° C. (wet) 46.3 46.8Compression After Impact 48.0 47.2 Strength, Ksi 23° C. Failure Strain,μin/in 5800 5900 Modulus, Msi 8.1 8.5 *Normalized to 62% fiber volume

The imide of PERA-1 was also mixed at a 35 weight % loading with theamide acid of PETI-5 in NMP at a concentration of ˜35% weight/weight. Tothis solution was added toluene and the mixture was heated under a DeanStark trap to remove the water of imidization. The PETI-5 imide powderprecipitated during this imidization. The mixture was poured into waterand the solid isolated and dried. This material exhibited an initialthermal melting transition at ˜149° C. and a T_(g) of 289° C. by DSCafter curing for one hour at 350° C. in a sealed aluminum pan. PETI-5cured under identical conditions exhibits a T_(g) of 250° C. and amelting transition at 387° C. The minimum complex melt viscosity was 315poise at 371° C. This minimum complex melt viscosity is an order ofmagnitude lower than that observed when the two imide powders werephysically mixed at the same concentration.

Favorable results were obtained from formulations of PERA-1 and an imideoligomer containing both pendent and terminal phenylethynyl groups witha calculated number average molecular weight of 5000 g/mole (designatedPTPEI-1). The preparation of PTPEI-1 is presented in FIG. 4. PTPEI amideacid in NMP and imide powder were prepared from3,4,3′,4′-biphenyltetracarboxylic dianhydride (BPDA) (0.91 mole),3,4′-oxydianiline (3,4′-ODA), 3,5-diamino-4′-phenylethynyl-benzophenone(DPEB) (0.15 mole) and 4-phenylethynylphthalic anhydride (PEPA) (0.18mole) according to the procedure previously reported by J. G. Smith,Jr., Adhesion Society Proceedings, Vol. 19, 29-32 (1996). PERA-1 in theimide form was physically mixed with imide powder of PTPEI-1 atconcentrations of 10, 20, and 50% by weight and the resultantformulation were characterized for complex melt viscosity and thermalproperties. The data is presented in Table 3.

TABLE 3 Characterization of Physically Mixed Imide Powders of PERA-1 andPTPEI-I Thermal Minimum Thermal Transition Complex Temp. of PERA-1PTPEI-1 Transition Temp., Melt Minimum Weight Weight Temp., ° C. ° C.Viscosity, Viscosity, % % Initial Cured* poise ° C. 100 0 191, 230 ND <1265 50 50 197 3236  7200 368 20 80 195 322 26300 368 10 90 195 318 37400361 0 100 231 307 150600 362 *Cured for 1 hour at 350° C. in a sealedaluminum pan. ND = Not detected by DSC.

Dramatic reductions in the minimum melt viscosity were observed withonly 10 weight percent of PERA-1 while the cured T_(g) increasedsubstantially.

Favorable results were also obtained from formulations of PERA-1 and animide oligomer containing pendent phenylethynyl groups with a calculatednumber average molecular weight of 5000 g/mole (designated as PPEI-1).The preparation of PPEI-1 is present in FIG. 5. PPEI-1 amide acid in NMPand imide powder were prepared from 3,4,3′,4′-biphenyltetracarboxylicdianhydride (BPDA) (0.91 mole), 3,4′-oxydianiline (3,4′-ODA) (0.85mole), 3,5-diamino-4′-phenylethynylbenzophenone (DPEB) (0.15 mole) andphthalic anhydride (PA) (0.18 mole) according to the procedurepreviously reported by J. W. Connell, J. G. Smith, Jr. And P. M.Hergenrother, Society for the Advancement of Materials and ProcessEngineering Proceedings, Vol. 41, 1102-1112 (1996). PERA-1 in the imideform was physically mixed with the imide powder of PPEI-1 atconcentrations of 10, 20, and 50% by weight and the resultantformulations were characterized for complex melt viscosity and thermalproperties. The data is presented in Table 4.

TABLE 4 Characterization of Physically Mixed Imide Powders of PERA-1 andPPEI-I Thermal Thermal Minimum PPEI- Transition Transition Complex Temp.of PERA-1 1, Temp., Temp., ° C. Melt Minimum Weight Weight ° C. Cured*(Melting Viscosity, Viscosity, % % Initial temp.) poise ° C. 100 0 182ND <1 270 50 50 149 ND 1308 369 20 80 149 270 (380) 10125 370 10 90 150268 (379) 13400 370 0 100 209 267 (380) 60000 371 *Cured for 1 hour at350° C. in a sealed aluminum pan. ND = Not detected by DSC.

PERA-1/PPEI-1 formulations exhibited similar trends as PERA-1/PETI-5 andPERA-1/PTPEI-1 formulations, but to a lesser degree with respect toreductions in melt viscosity and changes in thermal properties.

Favorable results were also obtained with formulations of PERA-2 andPETI-5 imide powders. Melt viscosity and thermal properties arepresented in Table 5.

TABLE 5 Characterization of Physically Mixed Imide Powders of PERA-2 andPETI-5 Thermal Thermal Minimum PETI- Transition Transition Complex Temp.of PERA-2 5, Temp., Temp., ° C. Melt Minimum Weight Weight ° C. Cured*(Melting Viscosity, Viscosity, % % Initial temp.) poise ° C. 100 0 179,235 ND <1 270 50 50 178 286 50 370 20 80 180 276 (385) 20000 371 10 90181 275 (384) 45000 370 0 100 235 250 (387) 56500 371 *Cured for 1 hourat 350° C. in a sealed aluminum pan. ND = Not detected by DSC.

Good results were also obtained with formulations of PERA-3 and PETI-5imide powders. Melt viscosity and thermal properties are presented inTable 6.

TABLE 6 Characterization of Physically Mixed Imide Powders of PERA-3 andPETI-5 Thermal Thermal Minimum PETI- Transition Transition Complex Temp.of PERA-3 5, Temp., Temp., ° C. Melt Minimum Weight Weight ° C. Cured*(Melting Viscosity, Viscosity, % % Initial temp.) poise ° C. 100 0 191,230 ND <1 265 50 50 197 ND 625 367 20 80 195 272 (384) 9990 369 10 90195 269 (381) 48300 371 0 100 235 250 (387) 56500 371 *Cured for 1 hourat 350° C. in a sealed aluminum pan. ND = Not detected by DSC.

Formulations of PERA-2/PETI-5 and PERA-3/PETI-5 exhibited similar trendswith respect to initial thermal transitions, cured T_(g) and reductionin melt viscosity as observed with PERA-1/PETI-5 imide powderformulations.

Having generally described the invention, a more complete understandingthereof can be obtained by reference to the following examples, whichare provided herein for purposes of illustration only and do not limitthe invention.

Synthesis of Phenylethynyl Containing Reactive Additives (PERAs) EXAMPLE1 Synthesis of PERA-1 from 3,5-Diamino-4′-phenylethynylbenzophenone (1.0mole), Phthalic Anhydride (1.0 mole) and 4-PhenylethynylphthalicAnhydride (1.0 mole)

Into a 3 L three-neck round-bottom flask equipped with a mechanicalstirrer, thermometer and reflux condenser was placed3,5-diamino-4′-phenylethynylbenzophenone (187.4 g, 0.60 mole), phthalicanhydride (88.9 g, 0.60 mole), 4-phenylethynylphthalic anhydride (148.9g, 0.60 mole) and glacial acetic acid (785 mL, 34% solids). The mixturewas heated to reflux (˜120° C.) to give a dark brown solution. After ˜2hours at this temperature a large amount of light tan precipitate formedmaking stirring impossible. Heating was continued for an additional hourand the reaction mixture was cooled to room temperature. The product wasisolated by filtration and washed three times in warm water to removeresidual acetic acid. The solid was air dried for ˜36 hours andsubsequently placed in a forced air oven at 125° C. for 15 hours. Thelight tan powder (397 g, 98% of theoretical yield) exhibited a meltingtransition at 182° C., and an exothermic transition due to the thermalreaction of the phenylethynyl groups beginning at 346° C. and peaking at381° C. as determined by DSC. The heat of the reaction was ˜275 J/g.

The amide acid of PERA-1 was prepared in a 3 L three-necked round-bottomflask equipped with a mechanical stirrer, nitrogen inlet and drying tubeusing 3,5-diamino-4′-phenylethynylbenzophenone (289.4 g, 0.926 mole),phthalic anhydride (137.2 g, 0.926 mole), 4-phenylethynylphthalicanhydride (230.0 g, 0926 mole) and NMP (1180 mL, 35% solids). Initially,the diamine was dissolved in 400 mL of NMP and the dianhydrides wereadded as a slurry in 250 mL of NMP. Additional NMP (350 mL) was used torinse in all of the solids. The mixture was stirred at room temperatureunder nitrogen for ˜72 hr (for convenience, this much time is notnecessary). This solution was used to prepare formulations with variousphenylethynyl containing oligomers.

EXAMPLE 2 Synthesis of PERA-2 from3,5-Diamino-4′-phenylethynylbenzophenone (1.0 mole), Phthalic Anhydride(1.5 mole) and 4-phenylethynylphthalic Anhydride (0.5 mole)

Into a 500 mL three-neck round-bottom flask equipped with a mechanicalstirrer, thermometer and reflux condenser was placed3,5-dimaino-4′-phenylethynylbenzophenone (23.43 g, 75.0 mmole), phthalicanhydride (16.66 g, 112.5 mmole), 4-phenylethynylphthalic anhydride(9.31 g, 37.5 mmole) and glacial acetic acid (125 mL, 30% solids). Themixture was heated to reflux (˜120° C.) to give a dark brown solution.After ˜2 hours at this temperature a large amount of light tanprecipitate formed making stirring impossible. Heating was continued foran additional hour and the reaction mixture was cooled to roomtemperature. The product was isolated by filtration and washed threetimes in warm water to remove residual acetic acid. The solid was airdried for ˜15 hours and subsequently placed in a forced air oven at 130°C. for 6 hours. The light tan powder (45.0 g, 96% of theoretical yield)exhibited a melting transition at ˜179° C. and 235° C., and anexothermic transition due to the thermal reaction of the phenylethynylgroups beginning at 346° C. and peaking at 383° C. as determined by DSC.The heat of the reaction was ˜209 J/g.

EXAMPLE 3 Synthesis of PERA-3 from3,5-Diamino-4′-phenylethynylbenzophenone (1.0 mole), Phthalic Anhydride(0.5 mole) and 4-Phenylethynylphthalic Anhydride (1.5 mole)

Into a 500 mL three-neck round-bottom flask equipped with a mechanicalstirrer, thermometer and reflux condenser was placed3,5-dimaino-4′-phenylethynylbenzophenone (21.98 g, 70.4 mmole), phthalicanhydride (5.211 g, 35.2 mmole), 4-phenylethynylphthalic anhydride(26.20 g, 105.5 mmole) and glacial acetic acid (200 mL, 20% solids). Themixture was heated to reflux (˜120° C.) to give a dark brown solution.After ˜2 hours at this temperature a large amount of light tanprecipitate formed making stirring impossible. Heating was continued foran additional hour and the reaction mixture was cooled to roomtemperature. The product was isolated by filtration and washed threetimes in warm water to remove residual acetic acid. The solid was driedin a forced air oven at 130° C. for 15 hours. The light tan powder(50.20 g, 99% of theoretical yield) exhibited a melting transition at˜191° C. and 230° C., and an exothermic transition due to the thermalreaction of the phenylethynyl groups beginning at 340° C. and peaking at374° C. as determined by DSC. The heat of the reaction was ˜281 J/g.

EXAMPLE 4 Resin from Physical Mixture of Imide Powders of PERA-1 (10% byweight) and PETI-5 (90% by weight)

Into a plastic vial was placed PETI-5 imide powder (4.5 g) and PERA-1imide powder (0.5 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 183° C. The material was cured forone hour at 350° C. in a sealed aluminum pan. Upon reheating, thematerial exhibited a T_(g) at 278° C. and a melting transition at 392°C. The material exhibited a minimum melt viscosity of 52,000 poise at˜371° C.

EXAMPLE 5 Resin from Physical Mixture of Imide Powders of PERA-1 (15% byweight) and PETI-5 (85% by weight)

Into a plastic vial was placed PETI-5 imide powder (4.25 g) and PERA-1imide powder (0.75 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 185° C. The material was cured forone hour at 350° C. in a sealed aluminum pan. Upon reheating, thematerial exhibited a T_(g) at 276° C. and a melting transition at 390°C. The material exhibited a minimum melt viscosity of 44,700 poise at˜371° C.

EXAMPLE 6 Resin from Physical Mixture of Imide powders of PERA-1 (20% byweight) and PBTI-5 (80% by weight)

Into a plastic vial was placed PETI-5 imide powder (4.0 g) and PERA-1imide powder (1.0 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 182° C. The material was cured forone hour at 350° C. in a sealed aluminum pan. Upon reheating, thematerial exhibited a T_(g) at 273° C. and a melting transition at 393°C. The material exhibited a minimum melt viscosity of 5600 poise at˜371° C.

EXAMPLE 7 Resin from Physical Mixture of Imide Powders of PERA-1 (35% byweight) and PETI-5 (65% by weight)

Into a plastic vial was placed PETI-5 imide powder (3.25 g) and PERA-1imide powder (1.75 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 183° C. The material was cured forone hour at 350° C. in a sealed aluminum pan. Upon reheating, thematerial exhibited no T_(g) or melting transition by DSC. The materialexhibited a minimum melt viscosity of 4700 poise at ˜372° C.

EXAMPLE 8 Resin from Physical Mixture of Imide Powders of PERA-1 (50% byweight) and PETI-5 (50% by weight)

Into a plastic vial was placed PETI-5 imide powder (2.5 g) and PERA-1imide powder (2.5 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 182° C. The material was cured forone hour at 350° C. in a sealed aluminum pan. Upon reheating, thematerial exhibited no T_(g) or melting transition by DSC. The materialexhibited a minimum melt viscosity of 500 poise at ˜371 ° C.

EXAMPLE 9 Resin from Physical Mixture of Imide Powders of PERA-1 (65% byweight) and PETI-5 (35% by weight)

Into a plastic vial was placed PETI-5 imide powder (1.75 g) and PERA-1imide powder (3.25 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 182° C. The material was cured forone hour at 350° C. in a sealed aluminum pan. Upon reheating, thematerial exhibited no T_(g) or melting transition by DSC. The materialexhibited a minimum melt viscosity of 53 poise at ˜371° C.

EXAMPLE 10 Resin from Physical Mixture of Imide Powders of PERA-1 (80%by weight) and PETI-5 (20% by weight)

Into a plastic vial was placed PETI-5 imide powder (1.0 g) and PERA-1imide powder (4.0 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 183° C. The material was cured forone hour at 350° C. in a sealed aluminum pan. Upon reheating, thematerial exhibited no T_(g) or melting transition by DSC. The materialexhibited a minimum melt viscosity of 21 poise at 373° C.

EXAMPLE 11 Resin from Physical Mixture of Imide Powders of PERA-1 (90%by weight) and PETI-5 (10% by weight)

Into a plastic vial was placed PETI-5 imide powder (0.5 g) and PERA-1imide powder (4.5 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 182° C. The material was cured forone hour at 350° C. in a sealed aluminum pan. Upon reheating, thematerial exhibited no T_(g) or melting transition by DSC. The materialexhibited a minimum melt viscosity of 14 poise at ˜270° C.

EXAMPLE 12 Resin from Mixture of Imide Powder of PERA-1 (20% by weight)and PETI-5 amide acid (80% by weight).

PETI-5 amide acid solution (7397.0 g of solution=2588.9 g of amide acid,35% solids in NMP) was placed in a large metal container and a solutionof PERA-1 (647.2 g, 35% solids in NMP) was added. The two solutions werestirred at room temperature under nitrogen for ˜16 hours. The resultinghomogenous solution exhibited a Brookfield viscosity of 8700 centipoise.This solution was used to prepare unidirectional carbon fiber (IM-7,unsized, 3 k tow) prepeg. The prepeg was subsequently used to preparelaminates in a vacuum press and in an autoclave using the followingprocessing cycle. The laminates were heated under vacuum at 250° C. andheld for one hour to remove volatiles and affect imidization. Pressure(50 psi) was subsequently applied and the laminate heated to 371° C. andheld for one hour. The laminate was cooled to room temperature underpressure and vacuum. Laminates processed under this cycle were wellconsolidated and void-free as evidenced by ultrasonic inspection.Mechanical properties of the composite laminates are presented in Table2.

EXAMPLE 13 Resin from Mixture of Imide Powder of PERA-1 (35% by weight)and PETI-5 amide acid (65% by weight)

PETI-5 amide acid solution (4051.0 g of solution=1417.9 g of amide acid,35% solids in NMP) was placed in a large metal container and a solutionof PERA-1 (777.0 g, 40% solids in NMP) was added. The two solutions werestirred at room temperature under nitrogen for ˜16 hours. The resultinghomogenous solution exhibited a Brookfield viscosity of 3000 centipoise.This solution was used to prepare unidirectional carbon fiber (IM-7,unsized, 3 k tow) prepeg. The prepeg was subsequently used to preparelaminates in a vacuum press and in an autoclave using the followingprocessing cycle. The laminates were heated under vacuum at 250° C. andheld for one hour to remove volatiles and affect imidization. Pressure(50 psi) was subsequently applied and the laminate heated to 371° C. andheld for one hour. The laminate was cooled to room temperature underpressure and vacuum. Laminates processed under this cycle were wellconsolidated and void-free as evidenced by ultrasonic inspection. Due tolow resin content in the prepeg (˜28-30%), mechanical properties werenot determined.

EXAMPLE 14 Resin from Mixture of Imide Powder of PERA-1 (50% by weight)and PETI-5 amide acid (50% by weight).

PETI-5 amide acid solution (1818.0 g of solution=727.2 g of amide acid,40% solids in NMP) was placed in a large metal container and a solutionof PERA-1 (724.2 g, 30% solids in NMP) was added. The two solutions werestirred at room temperature under nitrogen for ˜6 hours. The resultinghomogenous solution exhibited a Brookfield viscosity of ˜1000centipoise. This solution was used to prepare unidirectional carbonfiber (IM-7, unsized, 3 k tow) prepeg. The prepeg was subsequently usedto prepare laminates in a vacuum press and in an autoclave using thefollowing processing cycle. The laminates were heated under vacuum at300° C. and held for one hour to remove volatiles and affectimidization. Pressure (25 psi) was subsequently applied and the laminateheated to 371° C. and held for one hour. The laminate was cooled to roomtemperature under pressure and vacuum. Laminates processed under thiscycle were well consolidated and void-free as evidenced by ultrasonicinspection. Unidirectional laminates (6″×6″ 12 plies thick) werefabricated in an autoclave under 1-15 psi. The laminates appeared wellconsolidates, however ultrasonic inspection revealed poor to moderateconsolidation even though excessive resin flow was evident.

EXAMPLE 15 Resin from Amide Acid of PERA-1 (20% by weight) and PETI-5amide acid (80% by weight)

PETI-5 amide acid solution (7490 g of solution=2621.5 g of amide acid,35% solids in NMP) was placed in a large metal container and a solutionof PERA-1 (1855 g, 35% solids in NMP) was added. The two solutions werestirred at room temperature under nitrogen for ˜16 hours. The resultinghomogenous solution exhibited a Brookfield viscosity of ˜6800centipoise. This solution was used to prepare unidirectional carbonfiber (IM-7, unsized, 3 k tow) prepeg. The prepeg was subsequently usedto prepare laminates in a vacuum press and in an autoclave using thefollowing processing cycle. The laminates were heated under vacuum at250-300° C. and held for one hour to remove volatiles and affectimidization. Pressure (50 psi) was subsequently applied and the laminateheated to 371° C. and held for one hour. The laminate was cooled to roomtemperature under pressure and vacuum. Laminates processed under thiscycle were well consolidated and void-free as evidenced by ultrasonicinspection. Adhesive properties are presented in Table 4.

EXAMPLE 16 Resin from Physical Mixture of Imide Powders of PERA-1 (10%by weight) and PTPEI-1 (90% by weight)

Into a plastic vial was placed PTPEI-1 imide powder (0.50 g) and PERA-1imide powder (4.50 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 196° C. The material was cured for1 hour at 350° C. in a sealed aluminum pan. Upon reheating, the materialexhibited a T_(g) at 318° C. PTPEI-1 exhibits a T_(g) of 307° C. aftercuring for one hour at 350° C. in a sealed aluminum pan. The materialexhibited a minimum complex melt viscosity of 37400 poise at ˜361° C.PTPEI exhibited a minimum complex melt viscosity of 150600 poise at˜362° C.

EXAMPLE 17 Resin from Physical Mixture of Imide Powders of PERA-1 (20%by weight) and PTPEI-1 (80% by weight)

Into a plastic vial was placed PTPEI-1 imide powder (1.0 g) and PERA-1imide powder (4.0 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 150° C. The material was cured for1 hour at 350° C. in a sealed aluminum pan. Upon reheating, the materialexhibited a T_(g) at 322° C. PTPEI-1 exhibits a T_(g) of 307° C. aftercuring for one hour at 350° C. in a sealed aluminum pan. The materialexhibited a minimum complex melt viscosity of 26300 poise at ˜368° C.PTPEI exhibited a minimum complex melt viscosity of 150600 poise at˜362° C.

EXAMPLE 18 Resin from Physical Mixture of Imide Powders of PERA-1 (50%by weight) and PTPEI-1 (50% by weight)

Into a plastic vial was placed PTPEI-1 imide powder (2.50 g) and PERA-1imide powder (2.50 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 150° C. The material was cured for1 hour at 350° C. in a sealed aluminum pan. Upon reheating, the materialexhibited a T_(g) at 326° C. PTPEI-1 exhibits a T_(g) of 307° C. aftercuring for one hour at 350° C. in a sealed aluminum pan. The materialexhibited a minimum complex melt viscosity of 7200 poise at ˜368° C.PTPEI exhibited a minimum complex melt viscosity of 150600 poise at˜362° C.

EXAMPLE 19 Resin from Physical Mixture of Imide powders of PERA-1 (10%by weight) and PPEI-1 (90% by weight)

Into a plastic vial was placed PPEI-1 imide powder (4.50 g) and PERA-1imide powder (0.50 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 150° C. The material was cured for1 hour at 350° C. in a sealed aluminum pan. Upon reheating, the materialexhibited a T_(g) at 379° C. PPEI-1 exhibits a T_(g) of 267° C. and amelting transition at 379° C. PPEI-1 exhibits a T_(g) of 267° C. and amelting transition of 380° C. after curing for one hour at 350° C. in asealed aluminum pan. The material exhibited a minimum complex meltviscosity of 13,400 poise at ˜370° C. PPEI exhibited a minimum complexmelt viscosity of 60,000 poise at ˜371° C.

EXAMPLE 20 Resin from Physical Mixture of Imide Powders of PERA-1 (20%by weight) and PPEI-1 (80% by weight)

Into a plastic vial was placed PPEI-1 imide powder (4.0 g) and PERA-1imide powder (1.0 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 149° C. The material was cured for1 hour at 350° C. in a sealed aluminum pan. Upon reheating, the materialexhibited a T_(g) at 270° C. and a melting transition at 380° C. PPEI-1exhibits a T_(g) of 267° C. and a melting transition of 380° C. aftercuring for one hour in a sealed aluminum pan. The material exhibited aminimum complex melt viscosity of 10,125 poise at ˜370° C. PPEIexhibited a minimum complex melt viscosity of 60,000 poise at 371° C.

EXAMPLE 21 Resin from Physical Mixture of Imide Powders of PERA-1 (50%by weight) and PPEI-1 (50% by weight)

Into a plastic vial was placed PPEI-1 imide powder (2.50 g) and PERA-1imide powder (2.50 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 149° C. The material was cured for1 hour at 350° C. in a sealed aluminum pan. Upon reheating, no T_(g) ormelting transition was detected by DSC. PPEI-1 exhibits a T_(g) of 267°C. and a melting transition of 380° C. after curing for one hour at 350°C. in a sealed aluminum pan. The material exhibited a minimum complexmelt viscosity of 1308 poise at ˜369° C. PPEI exhibited a minimumcomplex melt viscosity of 60,000 poise at ˜371° C.

EXAMPLE 22 Resin from Physical Mixture of Imide Powders of PERA-2 (10%by weight) and PETI-5 (90% by weight)

Into a plastic vial was placed PETI-5 imide powder (4.50 g) and PERA-2imide powder (0.50 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 181° C. The material was cured for1 hour at 350° C. in a sealed aluminum pan. Upon reheating, the materialexhibited a T_(g) at 275° C. and a melting transition at 384° C. PETI-5exhibits a T_(g) of 250° C. and a melting transition of 387° C. aftercuring for one hour at 350° C. in a sealed aluminum pan. The materialexhibited a minimum complex melt viscosity of 45,000 poise at ˜370° C.PETI-5 exhibited a minimum complex melt viscosity of 56,500 poise at˜371° C.

EXAMPLE 23 Resin from Physical Mixture of Imide Powders of PERA-2 (20%by weight) and PETI-5 (80% by weight)

Into a plastic vial was placed PETI-5 imide powder (4.0 g) and PERA-2imide powder (1.0 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 180° C. The material was cured for1 hour at 350° C. in a sealed aluminum pan. Upon reheating, the materialexhibited a T_(g) at 276° C. and a melting transition at 385° C. PETI-5exhibits a T_(g) of 250° C. and a melting transition of 387° C. aftercuring for one hour at 350° C. in a sealed aluminum pan. The materialexhibited a minimum complex melt viscosity of 20,000 poise at ˜371° C.PETI-5 exhibited a minimum complex melt viscosity of 56,500 poise at˜371° C.

EXAMPLE 24 Resin from Physical Mixture of Imide powders of PERA-2 (50%by weight) and PETI-5 (50% by weight)

Into a plastic vial was placed PETI-5 imide powder (2.50 g) and PERA-2imide powder (2.50 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 178° C. The material was cured for1 hour at 350° C. in a sealed aluminum pan. Upon reheating, the materialexhibited a T_(g) at 286° C. and no melting transition was detected.PETI-5 exhibits a T_(g) of 250° C. and a melting transition of 387° C.after curing for one hour at 350° C. in a sealed aluminum pan. Thematerial exhibited a minimum complex melt viscosity of 50 poise at ˜370°C. PETI-5 exhibited a minimum complex melt viscosity of 56,500 poise at˜371° C.

EXAMPLE 25 Resin from Physical Mixture of Imide Powders of PERA-3 (10%by weight) and PETI-5 (90% by weight)

Into a plastic vial was placed PETI-5 imide powder (4.50 g) and PERA-3imide powder (0.50 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 195° C. The material was cured for1 hour at 350° C. in a sealed aluminum pan. Upon reheating, the materialexhibited a T_(g) at 269° C. and a melting transition at 381° C. PETI-5exhibits a T_(g) of 250° C. and a melting transition of 387° C. aftercuring for one hour at 350° C. in a sealed aluminum pan. The materialexhibited a minimum complex melt viscosity of 48,300 poise at ˜371° C.PETI-5 exhibited a minimum complex melt viscosity of 56,500 poise at˜371° C.

EXAMPLE 26 Resin from Physical Mixture of Imide Powders of PERA-3 (20%by weight) and PETI-5 (80% by weight)

Into a plastic vial was placed PETI-5 imide powder (4.0 g) and PERA-3imide powder (1.0 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 195° C. The material was cured for1 hour at 350° C. in a sealed aluminum pan. Upon reheating, the materialexhibited a T_(g) at 272° C. and a melting transition at 384° C. PETI-5exhibits a T_(g) of 250° C. and a melting transition of 387° C. aftercuring for one hour at 350° C. in a sealed aluminum pan. The materialexhibited a minimum complex melt viscosity of 9990 poise at ˜369° C.PETI-5 exhibited a minimum complex melt viscosity of 56,500 poise at˜371° C.

EXAMPLE 27 Resin from Physical Mixture of Imide Powders of PERA-3 (50%by weight) and PETI-5 (50% by weight)

Into a plastic vial was placed PETI-5 imide powder (2.50 g) and PERA-2imide powder (2.50 g). The two solids were physically mixed with aspatula for 10 minutes. The cap was placed on the vial and the vialshaken repeatedly to further mix the solids. The material exhibited aninitial thermal transition by DSC at 197° C. The material was cured for1 hour at 350° C. in a sealed aluminum pan. Upon reheating, no T_(g) ormelting transition was detected. PETI-5 exhibits a T_(g) of 250° C. anda melting transition of 387° C. after curing for one hour at 350° C. ina sealed aluminum pan. The material exhibited a minimum complex meltviscosity of 625 poise at ˜367° C. PETI-5 exhibited a minimum complexmelt viscosity of 56,500 poise at ˜371° C.

EXAMPLE 28

Synthesis of a phenylethynyl terminated amide acid and imide co-oligomerwith a calculated number average molecular weight of 1,000 g/mole using3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA, 0.5552 mole),1,3-bis(3-aminophenoxyphenyl)benzene (1,3-APB, 0.52 mole),9,9-bis(4-aminophenyl)fluorene (FDA, 0.33 mole),3,5-diamino-4′-phenylethynyl benzophenone (DPEB, 0.15 mole) and4-phenylethynylphthalic anhydride (PEPA, 0.8896 mole).

Into a 100 ml three neck round bottom flask equipped with a mechanicalstirrer, thermometer and nitrogen inlet/outlet was placed 1,3-APB(2.8263 g, 0.0097 mole), FDA (2.1379 g, 0.0061 mole), DPEB (0.8712 g,0.0028 mole) and 10 mL N-methyl-2-pyrrolidinone (NMP). Once dissolved, aslurry of BPDA (3.0371 g, 0.0103 mole) and PEPA (4.1058 g, 0.0165 mole)in 9 mL of NMP was added and rinsed in with an additional 10 mL of NMPto afford a solids content of 30.2%. The mixture was stirred overnightunder nitrogen (all solids had dissolved at this point). Toluene wasthen added (60 mL) and the reaction flask was fitted with a Dean Starktrap and reflux condenser. The mixture was heated via an oil bath to185° C. and held overnight. The toluene was removed from the system viathe Dean Stark trap (the reaction temperature eventually reached ˜205°C. during the toluene removal) and the reaction solution was allowed tocool to room temperature. The solution was poured into water in ablender to precipitate the oligomer. The solid was isolated byfiltration, washed in warm water (by placing in a large beaker andstirring) two times. The solid was allowed to air dry overnight andfurther dried in a forced air oven at ˜130° C. for ˜8 hours to give aquantitative yield of a tan powder. The powder exhibited an initialT_(g) of 162° C. and T_(m) of 210° C. and a T_(g) of 362° C. aftercuring for 1 hour at 371° C. The powder exhibited a complex meltviscosity of 185 poise at 250° C., this viscosity was stable at 250° C.for the duration of the experiment (1 hour). The powder exhibited acomplex melt viscosity of 40 poise at 280° C., this viscosity was stableat 280° C. for the duration of the experiment (2 hours). A neat resinmolding, approximately 1.5 inches in diameter and 25 mils thick, wasfabricated by heating the powder in an aluminum pan to 371° C. for 1hour in air. Based on a qualitative test of the molding, it wasmoderately tough.

EXAMPLE 29 Resin from Physical Mixture of Imide Powders of PERA-1 (10%by weight) and PTPEI described above (90% by weight)

Into a plastic vial was placed PTPEI (305-91-087) imide powder (2.67 g)and PERA-1 imide powder (0.30 g). The two solids were physically mixedwith a spatula for 10 minutes. The cap was placed on the vial and thevial shaken repeatedly to further mix the solids. The powder exhibitedan initial T_(g) of 160° C. and T_(m) of 196° C. and a T_(g) of 340° C.after curing for 1 hour at 371° C. The powder exhibited a complex meltviscosity of 90 poise at 250° C., this viscosity was stable at 250° C.for the duration of the experiment (1 hour). The powder exhibited acomplex melt viscosity of 35 poise at 280° C., this viscosity was stableat 280° C. for the duration of the experiment.

A carbon fiber laminate (10 inches by 24 inches, 36 plys thick, 44/44/12layup) was fabricated from this material by a resin infusion process.The laminate was well-consolidated and contained low void content.Specimens were machined from the laminate and tested for open holetension strength and open hole compression strength at temperaturesranging from room temperature to 600° F. The material exhibitedexcellent properties at both room temperature with good retention ofstrengths up to temperatures of 600° F.

While the invention has been described in terms of its preferredembodiments, those skilled in the art will recognize that the inventioncan be practiced with modification within the spirit and scope of theappended claims.

We claim:
 1. A cured film formed by adding a phenylethynyl reactiveadditive to a host phenylethynyl containing polymer, wherein thephenylethynyl reactive additive has a molecular weight less thanapproximately 1000 g/mol and is selected from the group consisting ofamide acid phenylethynyl reactive additives and imide phenylethynylreactive additives.
 2. A cured resin molding formed by adding aphenylethynyl reactive additive to a host phenylethynyl containingpolymer, wherein the phenylethynyl reactive additive has a molecularweight less than approximately 1000 g/mol and is selected from the groupconsisting of amide acid phenylethynyl reactive additives and imidephenylethynyl reactive additives.
 3. A cured adhesive formed by adding aphenylethynyl reactive additive to a host phenylethynyl containingpolymer, wherein the phenylethynyl reactive additive has a molecularweight less than approximately 1000 g/mol and is selected from the groupconsisting of amide acid phenylethynyl reactive additives and imidephenylethynyl reactive additives.
 4. A composite formed by adding aphenylethynyl reactive additive to a host phenylethynyl containingpolymer, wherein the phenylethynyl reactive additive has a molecularweight less than approximately 1000 g/mol and is selected from the groupconsisting of amide acid phenylethynyl reactive additives and imidephenylethynyl reactive additives.
 5. A cured film according to claim 1wherein the phenylethynyl containing host polymer is prepared from3,4,3′,4′-biphenyltetracarboxylic dianhydride, 3,4′-oxydianiline,1,3-bis(3-aminophenoxy) benzene, and 4-phenylethynylphthalic anhydride.6. A cured resin molding according to claim 2 wherein the phenylethynylcontaining host polymer is prepared from3,4,3′,4′-biphenyltetracarboxylic dianhydride, 3,4′-oxydianiline,1,3-bis(3-aminophenoxy) benzene, and 4-phenylethynylphthalic anhydride.7. A cured adhesive according to claim 3 wherein the phenylethynylcontaining host polymer is prepared from3,4,3′,4′-biphenyltetracarboxylic dianhydride, 3,4′-oxydianiline,1,3-bis(3-aminophenoxy) benzene, and 4-phenylethynylphthalic anhydride.8. A composite according to claim 4 wherein the phenylethynyl containinghost polymer is prepared from 3,4,3′,4′-biphenyltetracarboxylicdianhydride, 3,4′-oxydianiline, 1,3-bis(3-aminophenoxy) benzene, and4-phenylethynylphthalic anhydride.
 9. A cured film according to claim 1wherein the phenylethynyl containing host polymer is prepared from3,4,3′,4′-biphenyltetracarboxylic dianhydride, 3,4′-oxydianiline,3,5-diamino-4′-phenylethynylbenzophenone, and 4-phenylethynylphthalicanhydride.
 10. A cured resin molding according to claim 2 wherein thephenylethynyl containing host polymer is prepared from3,4,3′,4′-biphenyltetracarboxylic dianhydride, 3,4′-oxydianiline,3,5-diamino-4′-phenylethynylbenzophenone, and 4-phenylethynylphthalicanhydride.
 11. A cured adhesive according to claim 3 wherein thephenylethynyl containing host polymer is prepared from3,4,3′,4′-biphenyltetracarboxylic dianhydride, 3,4′-oxydianiline,3,5-diamino-4′-phenylethynylbenzophenone, and 4-phenylethynylphthalicanhydride.
 12. A composite according to claim 4 wherein thephenylethynyl containing host polymer is prepared from3,4,3′,4′-biphenyltetracarboxylic dianhydride, 3,4′-oxydianiline,3,5-diamino-4′-phenylethynylbenzophenone, and 4-phenylethynylphthalicanhydride.
 13. A cured film according to claim 1 wherein thephenylethynyl containing host polymer is prepared from3,4,3′,4′-biphenyltetracarboxylic dianhydride, 3,4′-oxydianiline,3,5-diamino-4′-phenylethynylbenzophenone and phthalic anhydride.
 14. Acured resin molding according to claim 2 wherein the phenylethynylcontaining host polymer is prepared from3,4,3′,4′-biphenyltetracarboxylic dianhydride, 3,4′-oxydianiline,3,5-diamino-4′-phenylethynylbenzophenone and phthalic anhydride.
 15. Acured adhesive according to claim 3 wherein the phenylethynyl containinghost polymer is prepared from 3,4,3′,4′-biphenyltetracarboxylicdianhydride, 3,4′-oxydianiline, 3,5-diamino-4′-phenylethynylbenzophenoneand phthalic anhydride.
 16. A composite according to claim 4 wherein thephenylethynyl containing host polymer is prepared from3,4,3′,4′-biphenyltetracarboxylic dianhydride, 3,4′-oxydianiline,3,5-diamino-4′-phenylethynylbenzophenone and phthalic anhydride.
 17. Acured film according to claim 1 wherein the phenylethynyl containinghost polymer is prepared from 3,3′,4,4′-biphenyltetracarboxylicdianhydride, 1,3-bis(3-aminophenoxyphenyl)benzene,9,9-bis(4-aminophenyl)fluorene, 3,5-diamino-4′-phenylethynylbenzophenoneand 4-phenylethynylphthalic anhydride.
 18. A cured resin moldingaccording to claim 2 wherein the phenylethynyl containing host polymeris prepared from 3,3′,4,4′-biphenyltetracarboxylic dianhydride,1,3-bis(3-aminophenoxyphenyl)benzene, 9,9-bis(4-aminophenyl)fluorene,3,5-diamino-4′-phenylethynylbenzophenone and 4-phenylethynylphthalicanhydride.
 19. A cured adhesive according to claim 3 wherein thephenylethynyl containing host polymer is prepared from3,3′,4,4′-biphenyltetracarboxylic dianhydride,1,3-bis(3-aminophenoxyphenyl)benzene, 9,9-bis(4-aminophenyl)fluorene,3,5-diamino-4′-phenylethynylbenzophenone and 4-phenylethynylphthalicanhydride.
 20. A composite according to claim 4 wherein thephenylethynyl containing host polymer is prepared from3,3′,4,4′-biphenyltetracarboxylic dianhydride,1,3-bis(3-aminophenoxyphenyl)benzene, 9,9-bis(4-aminophenyl)fluorene,3,5-diamino-4′-phenylethynylbenzophenone and 4-phenylethynylphthalicanhydride.
 21. A cured film according to claim 1 wherein thephenylethynyl reactive additive is prepared from3,5-diamino-4′-phenylethynylbenzophenone, and equal molar amounts ofphthalic anhydride and 4-phenylethynylphthalic anhydride.
 22. A curedresin molding according to claim 2 wherein the phenylethynyl reactiveadditive is prepared from 3,5-diamino-4′-phenylethynylbenzophenone, andequal molar amounts of phthalic anhydride and 4-phenylethynylphthalicanhydride.
 23. A cured adhesive according to claim 3 wherein thephenylethynyl reactive additive is prepared from3,5-diamino-4′-phenylethynylbenzophenone, and equal molar amounts ofphthalic anhydride and 4-phenylethynylphthalic anhydride.
 24. Acomposite according to claim 4 wherein the phenylethynyl reactiveadditive is prepared from 3,5-diamino-4′-phenylethynylbenzophenone, andequal molar amounts of phthalic anhydride and 4-phenylethynylphthalicanhydride.
 25. A cured film according to claim 1 wherein thephenylethynyl reactive additive is prepared from 1 mole of3,5-diamino-4′-phenylethynylbenzophenone, 1.5 moles of phthalicanhydride and 0.5 moles of 4-phenylethynylphthalic anhydride.
 26. Acured resin molding according to claim 2 wherein the phenylethynylreactive additive is prepared from 1 mole of3,5-diamino-4′-phenylethynylbenzophenone, 1.5 moles of phthalicanhydride and 0.5 moles of 4-phenylethynylphthalic anhydride.
 27. Acured adhesive according to claim 3 wherein the phenylethynyl reactiveadditive is prepared from 1 mole of3,5-diamino-4′-phenylethynylbenzophenone, 1.5 moles of phthalicanhydride and 0.5 moles of 4-phenylethynylphthalic anhydride.
 28. Acomposite according to claim 4 wherein the phenylethynyl reactiveadditive is prepared from 1 mole of3,5-diamino-4′-phenylethynylbenzophenone, 1.5 moles of phthalicanhydride and 0.5 moles of 4-phenylethynylphthalic anhydride.
 29. Acured film according to claim 1 wherein the phenylethynyl reactiveadditive is prepared from 1 mole of3,5-diamino-4′-phenylethynylbenzophenone, 0.5 moles of phthalicanhydride and 1.5 moles of 4-phenylethynylphthalic anhydride.
 30. Acured resin molding according to claim 2 wherein the phenylethynylreactive additive is prepared from 1 mole of3,5-diamino-4′-phenylethynylbenzophenone, 0.5 moles of phthalicanhydride and 1.5 moles of 4-phenylethynylphthalic anhydride.
 31. Acured adhesive according to claim 3 wherein the phenylethynyl reactiveadditive is prepared from 1 mole of3,5-diamino-4′-phenylethynylbenzophenone, 0.5 moles of phthalicanhydride and 1.5 moles of 4-phenylethynylphthalic anhydride.
 32. Acomposite according to claim 4 wherein the phenylethynyl reactiveadditive is prepared from 1 mole of3,5-diamino-4′-phenylethynylbenzophenone, 0.5 moles of phthalicanhydride and 1.5 moles of 4-phenylethynylphthalic anhydride.
 33. Acured film according to claim 1 wherein the phenylethynyl containinghost polymer is a co-polymer.
 34. A cured resin molding according toclaim 2 wherein the phenylethynyl containing host polymer is aco-polymer.
 35. A cured adhesive according to claim 3 wherein thephenylethynyl containing host polymer is a co-polymer.
 36. A compositeaccording to claim 4 wherein the phenylethynyl containing host polymeris a co-polymer.
 37. A cured film according to claim 1 wherein thephenylethynyl containing host polymer is an oligomer.
 38. A cured resinmolding according to claim 2 wherein the phenylethynyl containing hostpolymer is an oligomer.
 39. A cued adhesive to claim 3 wherein thephenylethynyl containing host polymer is an oligomer.
 40. A compositeaccording to claim 4 wherein the phenylethynyl containing host polymeris an oligomer.
 41. A cured film according to claim 1 wherein thephenylethynyl containing host polymer is a co-oligomer.
 42. A curedresin molding according to claim 2 wherein the phenylethynyl containinghost polymer is a co-oligomer.
 43. A cured adhesive according to claim 3wherein the phenylethynyl containing host polymer is a co-oligomer. 44.A composite according to claim 4 wherein the phenylethynyl containinghost polymer is a co-oligomer.
 45. A cured film according to claim 1wherein the phenylethynyl containing host polymer is in solution and thephenylethynyl reactive additive is in an amide acid solution.
 46. Acured resin molding according to claim 2 wherein the phenylethynylcontaining host polymer is in solution and the phenylethynyl reactiveadditive is in an amide acid solution.
 47. A cured adhesive according toclaim 3 wherein the phenylethynyl containing host polymer is in solutionand the phenylethynyl reactive additive is in an amide acid solution.48. A composite according to claim 4 wherein the phenylethynylcontaining host polymer is in solution and the phenylethynyl reactiveadditive is in an amide acid solution.
 49. A cured film according toclaim 1 wherein the phenylethynyl containing host polymer is in solutionand the phenylethynyl reactive additive is in an imide solution.
 50. Acured resin molding according to claim 2 wherein the phenylethynylcontaining host polymer is in solution and the phenylethynyl reactiveadditive is in an imide solution.
 51. A cured adhesive according toclaim 3 wherein the phenylethynyl containing host polymer is in solutionand the phenylethynyl reactive additive is in an imide solution.
 52. Acomposite according to claim 4 wherein the phenylethynyl containing hostpolymer is in solution and the phenylethynyl reactive additive is in animide solution.
 53. A cured film according to claim 1 wherein thephenylethynyl containing host polymer is a dry powder and thephenylethynyl reactive additive is a dry imide powder.
 54. A cured resinmolding according to claim 2 wherein the phenylethynyl containing hostpolymer is a dry powder and the phenylethynyl reactive additive is a dryimide powder.
 55. A cured adhesive according to claim 3 wherein thephenylethynyl containing host polymer is a dry powder and thephenylethynyl reactive additive is a dry imide powder.
 56. A compositeaccording to claim 4 wherein the phenylethynyl containing host polymeris a dry powder and the phenylethynyl reactive additive is a dry imidepowder.